Silver Jubilee review
25 years of progress in electrochemical methods
J. M. SYKES This review examines the electrochemical methods available to corrosion scientists today
and developments that have taken place in the past 25 years. The fundamental principles
of the methods are outlined and some practical difficulties explained.
The author is in the Department of Materials, University of Oxford, Parks Road,
Oxford, OX13PH, UK.
INTRODUCTION
The past 25 years have seen dramatic changes in the
character of instrumentation available to the electro-
chemist; the integrated circuit operational amplifier has
revolutionised the design of instruments!' 2 and the use of
digital electronics and computers, particularly the personal
computer, have enormously increased the scope and con-
venience of electrochemical experiments.3-5 These changes
have had an enormous-impact on the study of corrosion. In
many cases, fOr instance ac impedance, the basic principles
of the method were understood long ago,6. 7 but the equip-
ment which makes it possible to carry out useful measure-
ments, on complex corrosion systems, has only recently
been developed. Similarly, the experience necessary to
apply these techniques to complex corrosion problems
with confidence, and to interpret results reliably, has been
accumulated over the intervening period. 8-11
It is instructive to note that in the 1960 edition of
'Corrosion and oxidation of metals', U. R. Evans explains
in some detail how to carry out constant potential experi-
ments without an electronic potentiostat,12 although he
also draws attention to potentiostatic experiments by
Edeleanu.13 By 1965, when the first issue of British
Corrosion Journal was produced, the use of electronic
potentiostats in corrosion research was becoming
common.
It is inevitable, given the electrochemical nature of the
corrosion process, that much research uses electro-
chemistry as its main tool; it is also inevitable in a review
of this length that many fine pieces of work, with distinc-
tive and original features in their experiments, will be
omitted. It is not the aim here to review the extensive
range of techniques available to the electrochemist - there
are many excellent sources of such information;I4-16
instead, methods which have made an impact in the study
of corrosion will be highlighted and techniques in use
today critically compared. It is not intended that the
account be historical in nature or chronological in
sequence. For a broader perspective the reader is referred
to the proceedings of three conferences on 'Electro-
chemical methods in corrosion research' held in Europe
over the period 1982-1988.17-19
There are two main reasons for carrying out electroche-
mical experiments in the corrosion laboratory, or on site:
the first is to achieve a measurement of corrosion rate, the
second to characterise in some way electrochemical pro-
cesses contributing to, or limiting, the corrosion reaction.
In the former case it is to be preferred if the measurements
can be made continuously and without disturbing the
corrosion process. This type of experiment, used in corro-
sion monitoring or in the laboratory, will be discussed
below. First let us consider the routine electrochemical
measurements used to characterise corrosion processes.
POLARISATION CURVES
The use of potentiostats controlled by a computer or linear
scan generator is now a routine method for obtaining
potentiodynamic polarisation curves;20,21Tafel plots of the
resultant curves can be calculated and plotted with a
microcomputer, or made on a chart recorder through a
logarithmic amplifier. The latter method allows a greater
range of currents to be recorded without range changing,
but the former method is becoming predominant. If
computer measurements are taken via an autoranging
instrument the logarithmic amplifier offers no particular
advantage.
Rotating disc electrode
Albery relates how the measured current at an electrode
under free convection conditions is subject to many
extraneous influences, beyond the control of the
experimenter.22 This situation poses a problem for the
corrosion scientist, who is well aware that the corrosion
phenomena he or she wishes to study often take place in a
stagnant solution. If a flow is imposed on the test electro-
lyte, then the conditions are not the same as in the real
corrosion problem; however, if stagnant electrolyte is used
in the test cell, results are likely to be unreliable. (A
similar problem arises with the use of buffers; corrosion
usually occ~rs in unbuffered neutral solutions, whereas
electrochemistry is understood more readily if the pH can
be maintained constant.) Hougaard and Britz23 have con-
cluded that it is better to obtain reliable results under well
defined flow conditions, and so obtain corrosion measure-
ments that will represent an upper bound to the practical
corrosion rate, than to grapple with electrochemical meas-
urements under undefined hydrodynamic conditions.
Certainly this situation presents corrosion scientists with a
dilemma. The rotating disc electrode (RDE)14.15.24offers a
convenient means of controlling convection at the speci-
men and its use allows the production of reliable polarisa-
tion curves suitable for quantitative analysis.25-27 The
effect of varying the rotation speed upon the electrode
kinetics also provides a useful probe of mechanism. 24.27In
some studies alternative methods may be more
suitable. 28.29
Rotating ring disc electrode
It is convenient to interject some remarks on another
electrochemical technique at this point; if a detector elec-
trode, in the form of an ine'rt ring of well defined geo-
metry, is incorporated into a RDE, this ring electrode can
be used to detect soluble species formed during the corro-
sion process.30-34Quantitative measurements are possible,
so that if all the corrosion products are soluble, this
provides a direct measure of corrosion rate without any
interference with the specimen (the disc electrode) at all.
In circumstances where film growth and dissolution are
occurring simultaneously the rotating ring disc electrode
(RRDE) allows an independent measure of the dissolution
process.35 The RRDE is a powerful and underused
technique for corrosion studies.
Dr. Corros. J., 1990, Vol. 25, No.3 175
176 Sykes 25 years of progress in electrochemical methods

Ohmic potential drop (o )

Another problem which besets the experimenter carrying
out electrochemical experiments involving large currents,
or low conductivity media such as non-aqueous solutions
or dry concrete, is the potential difference which arises
between the surface of the specimen and the reference
electrode (or tip of the Luggin probe). This presents a
considerable difficulty in that the potential is not accu-
i
-I
4:
rately known, potential scan rates will change, depending
t=
upon the current, and in some instances potential regula- z
W
tion by the potentiostat may become unreliable. I-
Fortunately, modern instrumentation offers the means of o
a.. y
surmounting, or at least partially surmounting, these
difficulties.36 It should be mentioned that some potentio-
stat designs can avoid ohmic potential drops entirely, by
frequently interrupting the current for a period of micro-
seconds and sensing the potential only during this period. 37
One advantage of using ac or transient methods in corro-
sion studies is that they can measure and separate out
the ohmic contribution from the real electrochemical CURRENT ----+
characteristics of the specimen (see below).

PASSIVITY
The passive state has been extensively studied by electro-
chemical methods. 38.39One important area, relevant to
subjects such as pitting corrosion,40 or stress corrosion
cracking,41 is the kinetics of repassivation. This is one area
where high speed digital acquisition of results and data
processing by computers has permitted real advances to be
i
...J
4:
made.42 Detailed reviews have recently appeared t=
elsewhere. 43.44 z
W
I-
o
a..
CORROSION RATE MEASUREMENT
Polarisation resistance C2
Let us now consider the question of corrosion rate meas-
urements; these usually rely upon the reciprocal relation-
ship between corrosion current ieorr and polarisation
resistance Rp, arising from the Stern-Geary equation45

(1) CURRENT --.

a anodic reaction under activation control; b anodic reaction with

where ba and be are the Tafel slopes for the anodic and
cathodic reactions respectively. The constant B is defined
by equation (1). This relationship46 is only valid provided
that both anodic and cathodic reactions obey the Tafel
equation, that is
1]a = ba log(ia/io.a)
1]e= be log(iJio.e)
where 1]a and 1]e are overpotentials and io.a and io•e the
respective exchange current densities for anodic and cath-
odic reactions. It is because of these logarithmic depen-
dencies that the slope of a polarisation curve decreases as
current increases (Fig. 1a). If concentration polarisation is
present, such that the current tends to a limiting value
(Fig. 1b) then the slope d1]ldia will actually increase as the
anodic current increases. Note that the corrosion current is
higher at Y than at X in both diagrams, but in Fig. 1b the
value of Rp will actually have increased. Under these
circumstances, the Stern-Geary equation will be
unreliable.47
It should be noted that the charge transfer resistance
Ret' defined ih terms of the activation overpotential, rather
than the experimental overpotential, will still follow the
Stern-Geary equation and techniques, such as ac impe-
dance (see below), which can measure this quantity will
still supply valid measurements.48 It would be unusual,
given that the reversible potentials of anodic and cathodic
reactions are commonly over 1V apart, if both reactions in
the corrosion process were under activation control.
concentration polarisation
Effect of concentration polarisation on polarisation resistance
for anodic reaction under activation control and with concen-
tration polarisation: in both cases cathodic reaction C2 pro-
duces larger corrosion current, but whereas Rp is smaller at Y
than X in (a), it is not in (b)
(2)
(3) However, where the cathodic reaction is diffusion
controlled (a common circumstance, given the low solubi-
lity of oxygen in water), such that be = - 00 , and the anodic
reaction obeys the Tafel equation, then
(4)
It may not always he easy in practice to establish that the
theoretical requirements are met, but a pragmatic
approach, where the coefficient of proportionality is estab-
lished through empirical correlation of Rp measurements
with independent corrosion rate measurements (for
instance, weight loss), overcomes theoretical objection to
the technique. 47.49-51
Practical applications and sources of
error in processing results have been reviewed by Callow
et a/.52
One point that should be emphasised is that a linear
relationship between potential and current is not required
for the technique to be used. The slope of the polarisation
curve at Ecorr gives Rp, whether or not the relationship
between current and potential is linear. In many cases the
polarisation curve will give an approximate straight line,
for a region of 10-20 mV either side of Eeom and the

Dr. Corros. J., 1990, Vol. 25, No.3

 Sykes 25 years of progress in electrochemical methods 177

slope of this line (t!E/ t!i) is what is determined for instance, ac methods, where the impedance is calcu-
experimentally.47 lated from the amplitude of the ac current and the ampli-
Rewriting equations (2) and (3) in terms of the tude of the potential oscillation producing that current, a
corrosion current ieorrgives linear relationship between current and potential is
assumed, and perturbation must be kept small if measure-
ia = ieorrexp(2·303t!E/ba) (5) ments are to be valid; likewise with some dc or transient
procedures. One other important consideration is that
ie = ieorrexp( -2'303t!E/be) (6) polarisation resistance is intended to be a steady state
measurement. When measurements are made using
(where t!E is now a positive shift in potential from Eeorr), potentiodynamic techniques, such that the potential is
then the net anodic current flowing t!i is given by swept above and below the corrosion potential using a
triangular voltage ramp, errors will be introduced unless a
t!i = i - ic sufficiently slow scan speed is employed. 53.54When poten-
tial is varying, the current passing to the specimen consists
= icorr[exp(2·303t!E/ba) - exp( -2·303t!E/bc)] (7)
of two parts, the Faradaic current (driving the electro-
Each of the exponential terms can be expanded as a series, chemical reaction) and a charging current, which charges
for example the double layer capacity. The faster the scan rate, the
larger the charging current will be. For a valid measure-
ment the charging current must be negligible with respect
2.303 ) _ 2·303 !.-(2.303)2 to the Faradaic current, or Rp will be underestimated.
exp ( b t!E -1 + b t!E+ 2! b t!E
a a a Another difficulty arises where corrosion rates are high,
or measurements need to be made in high resistance

+ -1 (2.303
-- t!E )3 + ...
3! ba
For sufficiently small values of (2·303/ba)t!E, only the first
term need be considered (Le. the function can be treated
as linear), leading to:
In practice we also need to consider the second, quadratic
term; it is apparent then that equation (9) is exact only if
ba = be, where the quadratic terms cancel and cubic terms
can be neglected. Thus, unless ba = be, the polarisation
curve will not be accurately linear except for a very small
range near to the corrosion potential. A point not gener-
ally considered is that if t!i values are measured for two
potentials equidistant from the corrosion potential, and
the slope is calculated, it can readily be shown (see
Appendix) that, even when the polarisation curve is not
straight, the quadratic terms again cancel and the slope of
a line between the .limits of the scan will have the same
slope as the tangent at the corrosion potential (Fig. 2). In,
(8)
media. In these situations, the polarisation applied across
the metal/solution interface may be small compared to the
ohmic potential drop between the specimen and the refer-
ence electrode (or Luggin probe if in use). In this case the
polarisation resistance will be overestimated and too small
a value of corrosion current will be calculated.52 Even
when slope has been measured reliably, we need to ascer-
(9) tain the constant of proportionality B between icorrand Rp•
For some systems values of the constant have been
tabulated. 52,55In theory, a single determination of the
Tafel constants for the anodic and cathodic reactions is all
that is required to determine the value of B. However, as
the nature of the surface changes, or perhaps the nature of
the local environment, the values of these constants may
alter.52 Even where the relationship between the overall
weight loss in an experiment and the integrated corrosion
current has been tested, it will still be difficult to be
confident of the accuracy of instantaneous corrosion rate
measurements throughout the experiment. Methods have
now been developed that are able to continually determine
the Tafel parameters. Various authors have suggested
ways in which this can be achieved. 56-61

Curve fitting methods

i
l-
Z
If the Tafel equation describes both the anodic and catho-
dic reactions, then the experimental polarisation curve is
given by equation (7). The form of this current-potential
W
n:: slope =(9J...) = (-L) curve is fixed by the three parameters icom ba and be. By
n:: p taking values of 1] and i at three or more different points,
::> \ i.O R
U equations are obtained, which, when solved simul-
taneously, yield all three parameters. Of course, the accur-
acy of these measurements will depend upon the accuracy
of the determination of these individual points and noise,
for instance, will interfere with the accuracy of the result.
If regression analysis is used to fit the theoretical equation
to a whole set of experimental points, better accuracy will
result. The technique will be particularly efficient if a large
POTENTIAL --+ number of results are obtained using computer controlled
equipment, with statistical analysis performed by a
computer program. As with polarisation resistance, the
method relies on both anodic and cathodic reactions
adhering to the Tafel equation. Hougaard and Britz23have
reported that curve fitting produces accurate. corrosion
rates for zinc in a pH 5 buffer solution; however, although
~E a good fit was produced with copper in acid, the result was
incorrect. Skinner58 has examined the effect of experimen-
2 Polarisation curve illustrating that line joining points at poten- tal inaccuracies upon simple curve fitting routines and
tials equidistant from corrosion potential will have same slope concluded that use of an empirical B value in the
as tangent at corrosion potential (see also Appendix) Stern-Geary equation may actually give more reliable

Br. Corros. J., 1990, Vol. 25, No.3

178 Sykes 25 years of progress in electrochemical methods
results. In principle, a general equation for the polarisa-
tion curve, taking into account ohmic potential drops and
concentration polarisation, could be fitted to the experi-
mental curve and all the adjustable parameters deter-
mined, so that a generally valid method would be avail-
able, but the practical realisation of such a project presents
formidable difficulties.
Point of inflection
If ba = bc, the point of inflection in the polarisation curve
occurs at the corrosion potential, otherwise the line will
show curvature at this point.16 The point of inflection
represents another feature, readily identifiable on the
experimental curve, that can be used to arrive at a deter-
mination of corrosion current. Drazie and Vascie62 have
derived a relationship between the corrosion current and
the slope of the polarisation curve (di/ d1])PI at this point.
They suggest that errors arising through uncertainty in the
values of ba and bc can be reduced by using this method.
For instance, for iron in sulphuric acid at 298 K the use of
the relationship
(di)-d
icorr=22.2
1] PI
should not lead to errors greater than 20 allowing for
%
,
possible variations, in ba and bc' Similarly, Meszaros et
al.63 have derived a relationship between the de current at
this point il and the corrosion current. In this case har-
monic analysis (see below) serves to detect the point of
inflection, which corresponds to a minimum (theoretically
zero) in the second harmonic current. This current and ieorr
are related by
.= [(b~)2b~/(b~+b~)_ (b~) 2b~/(b~+ba].
l{ b' b' leorr
c a
b
where b~ = a/2·303 and = c/2·303. b~ b
For iron in acid this reduces to (approximately)
icorr = -0·6il•
AC impedance
AC impedance is a technique that has made rapid advance
since the 1960s; in particular, digital electronics have
facilitated much improved processing of results and
control of experiments, which simplifies the procedures. 8
Theoretical interpretation of the results has also made
great progress.11 Application of this method to corrosion
problems has become widespread and many authors have
described this technique (e.g. Refs. 10, 11, 39, 48, 55, 64-
66). Because ac methods use measurements of impedance
over a broad range of frequencies they can provide much
more information than simple de methods. Ultimately,
they rest upon the same foundation as polarisation resis-
tance methods, that is the assumption of linear depen-
dence of current upon potential, for small changes in
potential. Unless the signal is sufficiently small to meet this
condition the method will not be valid. Macdonald has
stressed the need for valid measurements to satisfy the
Kramers-Kronig relationships.l1 One attraction of the ac
method, using modern equipment, is that the use of a
periodic signal improves the signal/noise ratio for small
signals, so that reliable results can be obtained on systems
which would otherwise be difficult to measure using very
small perturbations. At a sufficiently low frequency, such
that the impedance is essentially a steady state measure-
ment, the modulus of the impedance IZI will equal the
polarisation resistance. Thus ac impedance provides an
alternative method for measuring corrosion rates. If meas-
urements are made at higher frequencies, the situation is
the same as for polarisation resistance measurements; that
is, when potential is changing there will be a charging
Dr. Corros. J., 1990, Vol. 25, No.3
(b)
(0)
c
-CJ- t
N
Rp
Z'-.
3 Simple circuit model for a corroding metal (a) with Nyquist
diagram that such a circuit will produce (b)
current in addition to the Faradaic current. This will be the
dominant component at high-frequencies. In the case of ac
measurements, because both the amplitude and phase of
the current sinusoidal response to a sinusoidal potential
perturbation are known, the relative contributions of these
two terms can be distinguished. The normal way of charac-
terising the behaviour of electrochemical systems in ac
experiments is in terms of model circuits composed of
passive elements (resistors, capacitors, and inductors),
. (10) plus a frequency dependent component, the Warburg
impedance, where diffusion phenomena are involved.66,67
The simplest type of model would be a resistor (the
polarisation resistance) in parallel with a capacitor (the
double layer capacitance), which corresponds to the sim-
plest physical situation at an electrode surface
(Fig. 3a).The response of this circuit on a Nyquist plot (Z"
the imaginary part of the impedance against Z' the real
part) is easily recognised as a semicircle (Fig. 3b). As
frequency increases, the impedance decreases and moves
along the semicircle toward the origin. At each point a
. (11)
vector from the origin describes the magnitude ('modu-
lus') and phase of the impedance at that particular fre-
quency. The diameter of the circle gives Rp• Even where
the experimental results fail to form a complete semicircle,
extrapolation to the real axis may permit determination of
Rp• The double layer capacitance can be calculated from
the frequency w at the top of the semicircle (Z" max-
imum), where RpC=w-1• The power of the technique
becomes clearer when we examine more complicated
model circuits. The simplest case is where the corrosion
process is occurring within a medium of significant ionic
resistance, such as a non-aqueous electrolyte * , or a solid
medium, like concrete or soil. The solid medium provides
a particular problem to the experimenter, because the
reference electrode cannot be positioned close to the
specimen surface. In this case the additional resistance of
the electrolyte appears as a simple displacement of the
semicircular response along the real axis (Fig. 4), which
can readily be subtracted from the result. (The impedance
response from concrete appears to be more complex than
a simple resistor, but fortunately careful ac measurements
can still separate the response of the specimen.) In those
instances where more complicated circuits are required to
* Chechirlian et ale have recently shown that misleading responses
can occur in such systems.68
(0) (b)
c
i
N
~
Rp
Rs Rs+Rp
z'--+
4 Model circuit incorporating solution resistance (RJ (a) and
effect on Nyquist diagram (b)

(0) (b)
c
Q Rp
N
i c
z'-+
5 Circuit model (a) and Nyquist diagram (b) for system exhibit-
ing diffusion impedance (W), in case of semi-infinite medium
(no convection)
simulate the electrode response, different interpretations
can be offered. For instance, where Nyquist plots show
two semicircles having different time constants, an expla-
nation can be advanced in terms of an electrochemical
reaction scheme, such as a two stage mechanism involving
an adsorbed intermediate69
A+e-~B
B+e-~C
An analysis of this case leads to various possible Nyquist
diagrams. The same results can equally well be interpreted
in terms of a physical model, where this seems more
appropriate. Examples would be localised corrosion at
pits,67or a coated metal with a polymer coating containing
pores.70
It must be emphasised that there will often exist differ-
ent model circuits which produce identical impedance
responses; we have no means, other than scientific judge-
ment, for establishing which is correct. There will always
be this inherent ambiguity; however, sometimes the com-
ponent values in these circuits will allow improbable
arrangements to be eliminated.
In the case where a diffusion impedance appears, the
low frequency response becomes dominated by this term
at sufficiently low frequencies. Sometimes (if the diffusion
boundary layer is of limited thickness), IZ I reaches a finite
limit which can be ascribed to Rp - although it is all too
apparent that the electrode reactions cannot now be des-
cribed as activation controlle~. In other examples (for
instance in concrete) IZI continues to increase, as pre-
dicted by theory, as the frequency falls (Fig. 5). No abso-
lute value of Rp can be determined in this situation. This
difficulty is not unique to ac impedance. Such specimens
would also fail to show a steady current under dc polarisa-
tion or would show increasing values of Rp as scan rate is
decreased in a potentiodynamic measurement. One possi-
bility in this situation is to select a particular frequency, or
scan rate, or time of polarisation, which - experience
shows - yields a good correlation between Z (or Rp) and
icom based upon an empirical choice of B. This practice has
been found to work well for steel in concrete. 55However,
as was discussed above, the idea of a polarisation resis-
tance arises from the consideration of activation controlled
electrode processes and that part of the impedance arising
from activation polarisation (the charge transfer resis-
tance) will provide a corrosion rate measurement resting
upon a sounder theoretical foundation.48 The proportiona-
lity constant B will in this case be calculable from the Tafel
coefficients for the system.
The same sort of difficulty arises in systems which
exhibit inductive loops, for instance iron in inhibited acid.
Here the charge transfer resistance is larger than the
polarisation resistance. Comparison of ac impedance
measurements with weight loss experiments has shown
that the charge transfer resistance yielded the better result
for corrosion rate.48
One problem that frequently arises with the ac tech-
nique is that the experimental results fail to conform to
Sykes 25 years of progress in electrochemical methods 179
(0) .
N
z'-+
6 Model circuit (a) for organic coating containing pores on metal
substrate and impedance response (b)
simple models of the types described above. A common
feature is that Nyquist plots do not show semicircles, but
'depressed semicircles' with the centre below the real
axis.64.65There are various explanations for this, based
upon the heterogeneity of the electrode, non-ideal capaci-
tances (for instances with organic coatings), or super-
imposed processes with multiple time constants.1l· 71
Rammelt and Reinhard have proposed that the depression
angle of the semicircle is related to roughness and can be
linked to the fractal dimension of the surface. 71 It may now
be necessary to use computer curve fitting methods in
order to extract accurate values for the circuit elements
and interpretation in terms of physical models becomes
more difficult. 72
Organic coatings
One area where impedance measurements have been
widely used is with organic coatings. 10. 70,73-76In principle,
the impedance of a coated metal should be the Slim of the
impedance of the coating and that of the electrode to
which it has been applied. In many cases the ac method
fails to distinguish these separate contributions and many
authors ascribe the response to the coating alone. Given
that high electrical resistance is a desirable characteristic
for a coating intended for corrosion protection, this would
in itself provide a useful measurement. AC techniques also
provide a measure of coating capacitance, which has been
related to the extent of water uptake77 - a further import-
ant parameter. The ac method is of most use, however,
where the coating contains pores, or is in the process of
breaking down, when the electrochemical behaviour at the
site of corrosion and the electrical behaviour of the coating
can be clearly resolved.73 The circuit model in Fig. 6a (Ref.
10) should lead to a Nyquist diagram of the form shown in
Fig. 6b, with the high frequency semicircle determined
chiefly by the resistance of the electrolyte in the pore and
the film capacitance, the low frequency semicircle by the
electrochemical reactions associated with corrosion.
Hepburn et ai. have used the capacitance associated with
the corrosion process to estimate the area of attack, so that
Rp could be connected to a local corrosion current
density.73 These experiments also showed that where solid
corrosion products block the pore, the interface response
becomes dominated by a Warburg impedance.
Br. Corros. J., 1990, Vol. 25, No.3
180 Sykes 25 years of progress in electrochemical methods
AC techniques
Various methods are available for ac measurements;
usually these are based on the application of a sinusoidally
varying current, or potential, and determining the poten-
tial or current response at each individual frequency of
interest. The phase and amplitude of the response can be
determined simply with an oscilloscope, or more usually
using phase sensitive detectors, such as lock-in amplifiers
or correlators. The 'electrochemical impedance
spectrum'lO is built up by making a large number of such
measurements over a wide range of frequencies, a task
which would require great perseverance, were it not for
automatic control of these instruments. Even so, each
measurement at each frequency must last for at least one
cycle, so that long periods of measurement may be needed
if results are required down to very low frequencies. One
way of reducing this problem is to make all the measure-
ments simultaneously, that is to perturb the sample with a
signal specially built up from a series of sine waves of
different frequencies. If the resultant current from the test
cell is subjected to Fourier analysis, Z for each separate
frequency can be determined.78 Any periodic waveform
can be broken down by Fourier analysis, so that suitably
chosen waveforms, for instance a square wave, can give
information across a range of frequencies. Keddam and
co-workers have investigated the relative accuracy of
different types of perturbation.79 In principle, sufficient
information is contained in one cycle, such as a single
potential pulse, to obtain a full impedance spectrum. In
practice, averaging over many cycles will help to eliminate
the problem of noise, inevitable with small signal
experiments.8o
Transient techniques
As outlined above, a single pulse contains, in principle, all
the information needed to generate an electrochemical
impedance spectrum,81 and computer analysis using the
technique of Laplace transformation can convert a current
transient, measured in the time domain, to an impedance
spectrum in the frequency domain.82 This approach has
great benefits in terms of speed: indeed, it may be the only
possible approach with systems that are evolving with
time, but lacks the ability to reject noise - so that the
accuracy of the final result (particularly at high frequen-
cies) can be much less than that from conventional ac
methods.79 The accuracy can be improved by averaging the
result of many individual pulse experiments, but then the
benefit of speed is lost. 80
The simplest pulse technique is the galvanostatic charg-
ing curve83 - for a system that can be represented by the
circuit in Fig.7a, the value of the series resistance Rs is
readily obtained from the initial instantaneous potential
rise; the electrochemical interface produces an exponen-
tial curve which yields Rp and Cd1 very readily (Fig. 7c)
(provided of course that potential perturbations are kept
small enough to give a linear response). An interesting
application is to in vivo corrosion measurements on metal
implants in rabbits.84 Even for circuits with a more com-
plex response, computer analysis can be used to elucidate
the various circuit parameters, for instance in the case of
steel in sea water, 85or in concrete. 86This method has been
successfully applied to corrosion monitoring of reinforced
concrete on site.87 Similar information can be gained from
current transients resulting from a potential pulse.88
Another approach is to analyse the potential relaxation as
the double layer discharges without external polarisation -
this is the basis of the coulostatic technique. 89.90The
simplest case is to use small charge pulses, so that the small
potential shifts which occur can be analysed in terms of
linear elements, but where the corrosion systems can be
described by a simple model circuit and the kinetics are
taken to obey the Tafel law , the analysis of large transients
Br. Corros. J., 1990, Vol. 25, No.3
(0)
c
Rp
(b)
Emax
-Ji
<!.-
j::w
z-
W'-
.-LL
oi
Q.tJ)
TIME-.
(c)
i
w
IX
E
w
E
a model circuit; b potential transient; c analysis of transient on
10g(Emax - E)-time plot: intercept = iRp, Emax = i(Rs + Rp), slope =
(RpC)-1
7 Potential - time response of simple electrode to current step
is also possible. Such experiments can generate Tafel plots
from a single pulse measurement.91
Potential relaxation methods have also been applied to
measurements on organic coatings and show an ability to
distinguish closely matched time constants in complex
impedance spectra.92-95Such methods also offer a useful
approach for the analysis of very slow time constants,
beyond the limit of normal ac equipment, although of
course all methods are vulnerable to potential drift super-
imposed on a transient.
Sleigh and McKinnon have recently suggested a new
approach to explpre the different relaxation processes in
complex systems, from potential transients.96 A plot of
- t( dEl dt) versus t yields a curve very similar to a phase
angle versus frequency plot from ac experiments. Modern
transient recorders and digital interfaces and the wide
availability of powerful microcomputers greatly facilitate
these methods.
Harmonic analysis
When linear circuit elements are subjected to a pure sine
wave potential perturbation, the current response is a pure
sine wave of the same frequency. However, the electro-
chemical response of a corroding metal will not be
perfectly linear; this results in the generation of harmonics
of the original frequency. Devay and Meszaros97-99have
developed equations to allow the corrosion rate to be
derived from measurements of the first, second, and third
harmonics of the Faradaic current. (It is important that the
frequency used for the measurement is such that non-
Faradaic charging currents are not taken into account.)

The advantage of this method is that the Tafel parameters
for the anodic and cathodic reactions need not be known,
nor need they remain constant with time. The signal
amplitude is not limited by the requirement of linearity.
An alternative approach is to detect the point of inflection
in the polarisation curve; that is, the point when the
second harmonic is zero, or a minimum. Meszaros has
derived a relationship between the dc current at that point
and the corrosion current (see above). 63Harmonic analysis
has been applied to metals with organic coatings and steel
in concrete.1OO-102
Electrochemical noise
This method offers one fundamental advantage: in princi-
ple, it offers the possibility (in the case of potential noise
measurements) of measuring corrosion rates and studying
corrosion phenomena without the need for any outside
disturbance of the corroding system. Iversonl03 first noted
the random potential shifts that occur with corroding
metals and was able to show that this 'noise' was decreased
below the threshold of measurement by addition of inhibi-
tor to the environment. Various authors have investigated
the possibilities of this technique.l04-l07 Epelboin et aI.108
have highlighted the need to avoid, or recognise the
presence of, spurious noise from electronic equipment.
The real noise signal may be generated by rupture
events in passive oxides, hydrogen gas evolution, or other
causes. A recent review noted the different shapes of
individual noise events which are seen to occur; some rise
quickly and fall slowly, in other cases they rise slowly and
fall abruptly. 109
In practice, shifts in potential ('potential noise') can be
measured, or currents passing when the potential is main-
tained constant ('current noise'). The simplest way to
quantify noise is by the standard deviation of the signal
about its mean value. Hladky and Dawson have suggested
that this may be used as a measure of corrosion ratel05 and
Searson and Dawson107and Harden et aI.110 have used this
method to measure corrosion rates in calcium hydroxide
solutions and concrete respectively. The validity of the
method was established through comparison with weight
loss and polarisation resistance measurements respec-
tively, though in both cases there is considerable scatter in
the results. There are still few published examples where
the technique has been used in practice.
A more sophisticated analysis of the noise can be
obtained by converting the time record into a power
spectrum by Fourier transformation. Bertocci has com-
puted electrochemic.al impedance spectra for corroding
electrodes from the ratios of power spectra of the current
and potential noise. 106 Hladky and Dawson105 and
Uruchurtu and Dawsonlll have used noise power spectra
>-
l-
v;
Z
w - ( I - --
o be
0::
W
~ _.
o - leorr!:lE
a..
O'l
o
log (FREQUENCY) --+
8 Schematic drawing of typical noise power spectrum: infor-
mation can be derived from the frequency at which 'roll off'
takes place, and slope of roll off105.107
Sykes 25 years of progress in electrochemical methods 181
as a means of recognising different forms of corrosion; a
typical noise spectrum is shown in Fig. 8. In practice, the
best way to measure noise may be the simplest, for
instance by measuring current noise between two identical
electrodes through a low value resistor. 112This reduces the
risk of extraneous noise from the instruments.
Although theoretical treatments exist,113.114the main
obstacle at present is in interpretation of results and
establishment of rigorous procedures by which quantita-
tive results can be extracted from the measurements, other
than by empirical correlation.
APPLICATIONS
Space is too limited here to deal specifically with individual
applications; the past 25 years has seen increasing use
of electrochemistry in the study of passivity,38,39
inhibitors, 115-118organic coatings,119-121 corrosion in
concrete,88 and many other areas.
Perhaps surprisingly, electrochemical methods are also
proving valuable in the study of atmospheric corrosion.121
Stratmann and Streckel have developed electrochemical
methods based upon the use of a Kelvin probe to sense the
potential beneath thin electrolyte films. 122.123
CONCLUSION
This paper has presented a corrosion scientist's viewpoint
on developments in the past 25 years; no doubt an electro-
chemist would have offered a different perspective. In
recent times, the corrosion scientist has been presented
with a bewildering array of new techniques, their propo-
nents clamouring for attention. Gradually the new meth-
ods have become established in research laboratories and
increasingly for application in the field. Together with in
situ spectroscopiesl4.15 and surface analysis outside the
environment,124 electrochemical methods have played a
major part in increasing our understanding of corrosion.
What of the future? There is little doubt that electro-
chemical methods will continue to playa major role in our
studies and that instrumentation used in research labora-
tories will find wider'use in the field; one area for develop-
ment is the use of photoelectrochemical methods in the
investigation of corrosion problems. 125Macdonald sees the
possibility of using non-linear regression analysis of ac
impedance measurements to determine the kinetic para-
meters for complex electrochemical mechanisms as an
important short term objective.ll
ApPENDIX
Calculation of Rp at Ecorr from two equidistant
potentials
Taking equation (8), neglecting cubic and higher terms,
and substituting into equation (7) gives
.
!:ll = 'eorr
. [(
1+
2·303
T 1 2.3032 !:lE 2)
!:lE +"2 ~
1 2.3032 !:lE 2)]
2·303
!:lE + "2 --2-
be
[ (2.303 2.303)
b + b
a e
. (AI)
If ba = be, this reduced to the Stern-Geary equation
. (A2)
On the other hand, if the current !:li' is calculated for
= - !:lE (without putting ba = be)
!:lE'
Br. Corros. J., 1990, Vol. 25, No.3
182 Sykes 25 years of progress in electrochemical methods

2.303 2.303) 32. B. MILLER: J. Electrochem. Soc., 1969, 116, 1117.

L1i' = icorr [ - L1E ( T +T 33. R. D. ARMSTRONG and A. C. COATES: Electroanal. Chem.
Interface Electrochem., 1974, 50, 303.
34. K. E. HEUSLER and C. FISCHER: Werkst. Korros., 1976, 27,
2 2
1 2(2.303 2.303 )] 697.
+2L1£ -b2 -~ . (A3) 35. A. M. RILEY and J. M. SYKES: Electrochim. Acta, 1990,35,35.
a c
36. D. BRITZ: J. Electroanal. Chern., 1978, 88, 309.

Rp can then be calculated from these two current measure- 37. P. GUTWILLENGER and G. SCHADE: Electrochim. Acta, 1979,
24, 1135.
ments as 38. S. HARUYAMA: Corros. Sci., 1990, 31, 29.
L1i - L1i' 39. C. GABRIELLI, M. KEDDAM, and H. TAKENOUTI: Corros. Sci.,
. (2.303 2.303)
lcorr -b- + -b- . (A4) 1990, 31, 129.
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cracks', (ed. A. Turnbull); 1987, London, HMSO.
ACKNOWLEDGMENT 44. J. R. AMBROSE: in 'Treatise on materials science and techno-
The assistance of my research students, past and present, logy', Vol. 23, 'Corrosion and aqueous processes and pas-
in scouring the literature for new methods and applying sive films', (ed. J. C. Scully); 1983, London, Academic
Press.
some of them in practice is gratefully acknowledged. 45. M. STERN and A. L. GEARY: J. Electrochem. Soc., 1953, 104,
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John Sykes gained a BA in Metallurgy at Cambridge University in 1964 and spent the next 6 years in research
there with Dr T. P. Hoar and Dr G. P. Rothwell. After academic appointments at the City University, London
and Sunderland Polytechnic, he moved to the Department of Materials in Oxford in 1978. His research group
has interests in pitting corrosion, stress corrosion cracking, corrosion in concrete, and organic coatings.
Sykes 25 years of progress in electrochemical methods 183
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